Photographic materials for the silver dyestuff bleaching process



United States Patent 3,454,402 PHOTOGRAPHIC MATERIALS FOR THE SILVERDYESTUFF BLEACHING PROCESS Walter Anderali, Marly-le-Grand, Rudolf Mory,Dornach,

and Bernhard Piller, Marly-le-Grand, Switzerland, assignors to CibaLimited, Basel, Switzerland, a Swiss company No Drawing. Filed Oct. 5,1965, Ser. No. 493,269 Claims priority, application Switzerland, Oct. 8,1964 13,108/ 64 Int. Cl. G03c 1/10 US. C]. 96-99 7 Claims ABSTRACT OFTHE DISCLOSURE Photographic material for the silver dyestufi bleachingprocess which contains in one layer silver halide and at least onedyestutf having a magenta tint. The dyestuif corresponds to the formula.

OH HO HOQIS S OaH in which X and X each represents a member selectedfrom the group consisting of a hydrogen atom and a sulfonic acid group,Y and Y each represents a member selected from the group consisting of aphenylamino group further substituted by alkyl groups in the twopositions vicinal to the bond with the nitrogen atom, an alkylaminogroup a hydroxyalkylamino group having at least two carbon atoms and acycloalkylamino group, R and R each represents a cyclic radicalcontaining at least one benzene ring to which the azo group is attached,and A represents a member selected from group consisting of the radicalof the formula -CO-- and the diacyl radicals of benzene-, thiopheneandfurandicarboxylic acid and cyanuric acid. Dyestufis of this type displayadvantageous absorption curves in respect of position and configuration,have a. good water-solubility and are fast to diffusion.

The present invention provides photographic materials for the silverdyestuff bleaching process, which materials have specially valuableproperties. They contain in one layer at least one dyestufi which, likethe dyestuif of the formula corresponds to the general formula OH HOSOzH in which X and X each represents a hydrogen atom or a sulfonic acidgroup, Y and Y each represents an amino group, of which at least one isa secondary or tertiary amino group, R and R each represents a cyclicradical containing at least one benzene ring to which the azo group isbound and A represents the radical of the diamide of a carbon-containingacid which is at least dibasic, which residue is bound to R and Rthrough the nitrogen atoms.

The dyestuffs of the Formula 2 can be prepared in known manner. Anadvantageous procedure is to couple a. diazo compound of the benzeneseries which contains an H N group and which does not couple with itselfor a diazo compound of the benzene series which contains a groupconvertible into an H N group, with an amino hydroxynaphthalene sulfonicacid of the formula in which X and Y have the meanings given above, andif necessary, after conversion of the above-mentioned group into the H Ngroup, to condense the aminorn onoazo dyestuff in a molecular ratio of2:1 with a halide of a carbon-containing acid which is at least dibasic.In order to increase the size of the dyestulf molecule, it is rn on,330- on: 1%111 H1 -oc- -oo-1 n 111% N=N N=N 0H HOa S S0311 Ho- H033 sourpossible first to acylate the aminomonoazo dyestuff with anitrobenzenemonocarboxylic acid halide, to reduce the nitro compound toan amino compound, and only then to condense the aminoazo dyestuff withthe halide of the polybasic acid.

Coupling components to be used in the manufacture of the dyestuffs aretherefore 2-amino-8-hydroxynaphthalene-3,6-disul'fonic acids orpreferably 2-amino-8-hydroxynaphthalene-6-sulfonic acids having an aminogroup that is further substituted. If the amino group is furthersubstituted by a phenyl radical, the latter must contain a substituent,for example, a methyl group or a chlorine atom, at both positionsvicinal to the bond with the nitrogen atom. The amino group may also bea monoalkyl or dialkyl amino group, a (monoor di-hydroxyalkyl)-aminogroup or an alkyl-hydroxy-alkyl-amino group, which aliphatic,further-substituted amino groups contain at least 2 carbon atoms. Alsosuitable are cycloalkylamino groups, for example the cyclohexylaminogroup. The following compounds may be mentioned as examples of couplingcomponents: 2- (2, 6-dimethylphenylamino) 8-hydroxynaphthalene-6-sulfonic acid, 2- (2',6-diethylphenylamino 8-hydroxynaphthalene-6-sulfonic acid,2-(2',4,'6'-trimethylphenylamino)-8-hydroxynaphthalene-6-sulfonic acid,2-(2',3',4,6'-tetramethylphenylamino)8-hydroxynaphthalene-6-sulfonicacid, 2-dimethylamino-8hydroxynaphthalene-6-sulfonic acid,2-diethylaminlo-8-hydroxynaphthalene6-sulfonic acid,Z-fl-hydroxyethylamino-8hydroxynaphthalene-6-sulfonic acid, 2-di,B-hydroxyethyl amino) 8-hydroxynaphthalene-6- sulfonic acid,2-n-butylamino-8-hydroxynaphthalene-6-sulfonic acid,

4 IITH:

-N=N NH:

10 The aminomonaz'o dyestuflfs obtained in the manner indicated or theaminobenzoylamino compounds obtained by acylating the acid dyestuflswith, for example, metaor para-nitrobenzoyl chloride and subsequentreduction are condensed, for example, with the following halides ofcarbon-containing acids which are at least dibasictben-Zene-1,3-dicarboxylic acid dichloride, benzene-1,4-dicarboxylic aciddichloride, diphenyl-(1,1')-4,4-dicarboxylic acid dichloride,furan-2,5-dicarboxylic acid dichloride, thiophene-Z,S-dicarboxylic aciddichloride, phosgene (dichloride of carbonic acid) and cyanuric chloride(trichloride of cyanuric acid). Symmetrical dyestuffs are obtainable aswell as asymmetrical dyestufls, especially with cyanuric chloride.

All the reactions involved in the manufacture of the dyestuffs of theFormula 2 can be carried out in known manner. As has been indicated inthe foregoing, dyestutfs that are particularly suitable for the purposein question are:

(I) Dyestuffs of the Formula 2, in which X, X, R R and A have themeanings given above and Y and Y represent amino groups, of which atleast one is a phenylamino group further substituted in the phenylradical at the two positions vicinal to the bond with the nitrogen atom.

Dyestuffs of the kind defined that are Worthy of special mention arethose of the formula HaC HOBIS stuffs may be prepared whose radicalsderived from the diazo components correspond to the formula in which Rrepresents a phenylamino group further substituted in the phenyl radicalat least in the two positions vicinal to the bond with the nitrogenatom,

NH-A-HN- represents the radical of the diamide of a carbon-containingacid that is at least dibasic and n represents an integer not greaterthan 2. This applies in particular to dyestuffs of the formula in whichNHAHN-- has the meaning given above and R represents a hydrogen atom ora methyl group. (II) Dyestuffs of the Formula 2, in which 'X, X, R

R and A have the meanings given above and Y and Y represent aminogroups, of which at least one is an alkylamino or hydroxyalkylaminogroup having at least two 6 carbon atoms or a cycloalkylamino group,especially the The layer dyestuffs of the Formula 2 display veryaddyestutfs of the formula vantageous behaviour in the silver dyestutfbleaching proc- 9 O NH A HN ran-Q n-1 tun-1 Q-Ndt 0H Hots HOaS H0- HOaSH035 in which Y represents an alkylamino or hydroxyalkyless. Theirabsorption curves are advantageous in respect ammo r p having at leasttwo carbon atoms or a y eof position and configuration, the maxirnabeing within glkylamlllllo E ?P the desired range and subsidiaryabsorption being miniue of t e dlamlde of a car on'contammg am at 18 atmal. Notwithstanding their good solubility in wat erfmost iii: zdlabaslcand n represents an Integer not greater of the dyestuffs difiuse onlyvery slightly. The dyestuffs Like the dyestuffs themselves, thephotographic layers which are specially resistant to diffusion arethose. of the Formulae 20 to 25. In cases where additives are requiredwhich, in accordance with the invention, contain at least one dyestuffof the Formula 2, may be prepared in known to prevent diffusioncompletely, for example, guanidines,

manner and used for the pro n f ol r g 20 the said additives do notimpair the fastness to light of The y 0f the F01'm111a generally have athe dyestuffs of the Formula 2; to be used in accordance genta tint inthe gelatme, and they may advantageously be with the invention 7 Presentm the gmen'sensltwed sllver hahde'gelaune emul All the magenta dyestuifslisted in the following and sion layer in multilayer material, whichmaterial also contains a red sensitized cyan emulsion layer and a yellowwhich correspond to the general Formula Zmay be manuemulsion layer thathas not been specially sensitized. factllred by e m th ds d ri d a ve:

' H H Ha OH; HO CE 2 a NH. HN-O C-g --C 0-NH HN g N=N N=N OH HO] S 03HHO HOa S 0 H Ha CH: Ha OH:

H HN

N=N NH-O (JO-47 o-nNGm-m I OH HO: 803E HO Ha CH: H: CH1

EN EN 0 OH 1102 5 503E HO Ha CHI Hi0 OH;

I C-UH NE HN- H1 1 Q OH H018 01H H0 1 l 1 2 The following table showshow the position and con- 4 grams of potassium bromide and 0.3 gram ofbenzfiguration of the dyestutf absorption curve can be changed triazole.by the choice of bridging groups, coupling component and (2) Washingwith water for 5 minutes. di component R 1 (3) Fixation for 6 minutes ina solution of 200 grams 5 of crystallized sodium thiosulfate and 20grams of potas- Dyestuif of the formula: Absorption maximum 1 m i bilfit i 1 li of waten 1 562 (4) Washing with water for 5 minutes. 11 570(5) Color bleach for 3 to 12 minutes with a solution 14 '57 whichcontains, per liter of Water, 50 to 80 grams of potas- 20 552 siumbromide, 40 to 80 grams of thiourea, 35 to 80 grams 21 64 of sulfuricacid of 30% strength and, if desired, 0.001 22, 569 gram ofZ-aminohydroxyphenazine. 23 562 (6) Washing with water for 10 minutes.24 570-580 (7) Bleaching of residual silver for 5 minutes with a 25 v580 solution of 60 grams of crystallized copper sulfate, 80 Measurementsmade when the dyestuft is dissolved in grams of Potasslum bromlde and 15of hydrochlonc gelatine. acid of 30% strength in one liter of water.

EXAMPLE (8) Washing with water for 5 minutes.

(9) Fixation for 5 minutes in the manner indicated The following layersare applied in the sequence munder dicated to a substrated white, opaqueacetate film: (10) Washing with Water f 5 minutes (1) A red-sensitizedsilver bromide emulsion in gela- A true i i image to b viewed inincident light tine which contains the cyan dyestuif of the formula andwhich is resistant to light is obtained.

( 6) O-CO-HN on o-om H0 un-oo-O (2) A colorless gelatine layer withoutsilver halide. The magenta dyestuffs of the Formulae 10 to can (3) Agreen-sensitized silver bromide emulsion in gelabe incorporated in thegreen-sensitized layer instead of tine which contains the magentadyestuff of the Forthe dyestuff of the Formula 1, and similar goodresults mula 1. are obtained thereby.

(4) A yellow filter layer which contains the dyestuff 5 What is claimedis: of the formula 1. Photographic material for the silver dyestufrbleach- Cl mg process which contains in one silver halide layer at 27least one dyestufi of the formula N CH=C I S0311 N=NR1NHAHN-R1'N=N H3 OHHO (5) A blue-sensitized silver bromide emulsion in gelatine whichcontains the yellow dyestuif of the formula 40 H035 SOaH 8) 11035 HstllCH3 Slo n WA NHC CHNQMM ()CH3 HaC-O l SIO3H H038 The gelatine layers mayalso contain additives, for eX- in which X and X each represents amember selected ample, wetting agents, hardening agents and stabilizersfrom the group consisting of a hydrogen atom and a for the silverhalide. The quantities of materials used SulfOmC a p, Y and fiachTepfesellls a member are such that each layer contains 0.5 gram ofdyestuff and Selected from the P Conslstlng of p y Q- silver bromidecorresponding to 1 to 1.2 grams of silver P P substltumd y l y groups Inthe two POSI- per squaremeter f film trons vicmal to the bond with themtrogen atom, an

alkylamino group, a hydroxyalkylamino group having 0 it leasg two carbonatoms and a cycloalkylamino group, 1 an R each re resents a c clicradical containin 15 then developed m the followl ng manner: at leastone benzene ring to .whizh the azo group is at Development for 6 mlnutesm a bath contammg tached, and A represents a member selected from groupPfi lltel' Of Water, 50 grams of anhydrous Sodium 5111' consisting ofthe radical of the formula --CO and fate, gram of -p y -py 6 grams f thediacyl radicals of benzene-, theopheneand furanhydroquinone, 35 grams ofanhydrous sodium carbonate, dicarboxylic acid and cyanuric acid.

The film so prepared is exposed beneath a colored diapositive to red,green and blue light. The reproduc- 13 14 2. Photographic material asclaimed in claim 1 which and a cycloalkylamino group. A represents'amember contains silver halide and a dyestuff of the formula selectedfrom group consisting of the radical of the for- HN-R, Rz-NH NH-A-HN -OHH-Oa S S OaH HOzS HOa S in which R represents a phenylamino groupfurther mula -CO- and the diacyl radicals of benzene-, thiosubstitutedby methyl groups in the phenyl radical at pheneand furan-dicarboxylicacid and cyanuric acid, least in the two positions vicinal to the bondwith the and n represents an integer not greater than 2.

nitrogen atom, A'represents a member selected from 4. Photographicmaterial as claimed in claim 1 which group consisting of the radical ofthe formula CO 20 contains silver halide and a dyestufi of the formulaE30 CH3 H3 CH3 NH EN OH 035 503E HQ Hess S 03H and y i 0f be11 Zel1ej,thiopheneand 40 in which A represents a member selected from groupfuran-dicarboxyllc acid and cyanurrc acid, andnrepresents consisting ofthe radical of the formula and an integer not greater than 2.

3. Photographic material as claimed in claim 1 which the diaWl radicalsof nzene, thiopheneand furancontains silver halide and a dyestuif of theformula dicarboxylic acid and cyanuric acid, and a represents a Y1 Y1NH-A-HN N=N- -N=N 0H S OaH 11048 HO s0=H H083 in which Y represents amember selected from the the group consisting of a hydrogen a om an a mey group.

gmup Qonslstmg of an aliiylammo group a hydroxy 60 5. Photographicmaterial as claimed in claim 1 which alkylammo group each having at leastWO Carbon atoms contains silver halide and the dyestufi of the formulaH3O CH; Ha CHa 16 6. Photographic material as claimed in claim 1, whichcontains the dyestuff of the formula CH3 Halo H3C- CH3 H30 07H;

1%IH 1103 s 503E HN N=NC -N=N i? I OH 1511-00-0 0-0 O-HN HO I S H0 8S0311 7. Photographic material as claimed in claim 1, which contains thedyestuff of the formula 20 E 0 CH3 i V H3O CH3 +11 HN N=NONHOC-QNH-E-JENOC O-HN-Q-N=N OH Hoa s H045 HO H035 HOaS References CitedUNITED STATES PATENTS 3,211,554 10/1965 Dreyfuss 9699 J. TRAVIS BROWN,Primary Examiner.

US. 01. X.R. 96-20, 53, 73

CERTIFICATE OF CORRECTION Patent No. 3:5'h Dated July 8, 1969Inventor-(5) WALTER ANDERAU ET AL It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

(Tolumn 13, the formula, after line 2, should appear as follows:

. NH A HN N M 0 0 H g 11 OH 0 Column 13, the formula, after line ML,should appear as follows:

NH A-- HN EN OH O O HO SO3H H0 8 1 HO. S SO H v n l n 5 Signed andsealed this 17th day of August 1 971 (SEAL) L Attest:

EDWARD M.FLETCHER,JR. Attesting Officer WILLIAM E. SCHUYLER, JR.Commissioner of Patents

